CN102989522B - Porous cement-based photocatalytic material and preparation process thereof - Google Patents
Porous cement-based photocatalytic material and preparation process thereof Download PDFInfo
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- CN102989522B CN102989522B CN201210546856.XA CN201210546856A CN102989522B CN 102989522 B CN102989522 B CN 102989522B CN 201210546856 A CN201210546856 A CN 201210546856A CN 102989522 B CN102989522 B CN 102989522B
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Abstract
The invention discloses a porous cement-based photocatalytic material and a preparation process thereof. The porous cement-based photocatalytic material is prepared from a porous cement-based carrier, an interface processing agent and a photocatalytic agent. The preparation method comprises the following steps of pre-treatment of the porous cement-based carrier, interface activation treatment of the porous cement-based carrier, dispersion of the photocatalytic agent, loading of the photocatalytic agent and post-treatment of materials. The porous cement-based photocatalytic material and the preparation process thereof have the advantages that an ultrasonic pore opening manner is adopted to improve the through-hole rate of a porous cement-based material; a manner of combining the interface treatment and the negative-pressure loading is used for activating the surface property of the porous cement-based material and improving the loading amount and the uniformity, so as to improve the photocatalytic efficiency and the long-period activity; and furthermore, a coordination effect of the porous cement-based material and the photocatalytic material is combined to improve the treatment capability on harmful gas.
Description
Technical field
The present invention relates to novel environment friendly functional architecture field of material technology, be specifically related to a kind of honeycombed cement base optic catalytic material and preparation technology thereof.
Background technology
Honeycombed cement sill is a kind of novel environment friendly functional architecture material that developed recently gets up, and it has the various functions such as lightweight, sound insulation, heat-insulation and heat-preservation.At present, honeycombed cement sill is mainly used in the aspect such as wallboard, house insulation, compensation ground and roofing side slope within doors, and it is more extensive that the good characteristic of honeycombed cement sill will make it apply.Honeycombed cement sill generally has abundant hole, can adsorb a large amount of pernicious gases, but it does not possess to gas cleaning function, therefore the ability of its process pernicious gas is also limited.
Photocatalysis purifying technology is a kind of new technique thinking processing air pernicious gas and water pollution proposed in recent years, and its purifying without selecting to degrade pollutant, the feature of non-secondary pollution etc., makes it possess wide development and application space.Current, one of bottleneck of photocatalysis purifying technology large-scale application mainly the choosing of load carriers; Existing catalysis material and cement-based material complex technique, mainly prepare the little cement-based material of porosity, generally that photochemical catalyst and cement raw material are carried out blended preparation, so not only cause a large amount of catalysis materials wrap up by hydrated cementitious material and lose photocatalytic activity, in addition, because cement matrix interior lights catalysis material can not touch light source, also make material monolithic photocatalytic activity lower.
Chinese patent CN 102557723 A discloses foam concrete of a kind of nitrogen-doped titanium dioxide and preparation method thereof, and modified light catalyst and Portland cement sill, blowing agent etc. have been mixed with a kind of honeycombed cement base optic catalytic scavenging material by this technology.The modification of catalysis material has certain effect to its visible ray utilization rate of raising and photocatalytic activity, but owing to being in the process preparing honeycombed cement sill, catalysis material is added wherein, be unfavorable for the dispersion of catalysis material, make a large amount of catalysis material wrap up by hydrolysis product of cement, in addition, because Portland cement sill light transmitting property is poor, hydrated product is closely knit, cause wrapped catalysis material and can not get Appropriate application, waste catalysis material in a large number, the photocatalysis efficiency of material is also reduced while improve the use cost of catalysis material.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of honeycombed cement base optic catalytic material, has noxious pollutant function in Cleaning Air and water body, environmental friendliness, and to environment non-secondary pollution.
Another object of the present invention is to provide a kind of preparation technology of honeycombed cement base optic catalytic material.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of honeycombed cement base optic catalytic material, it first in interface treating agent, carries out pretreatment by honeycombed cement base carrier, then carries out with photochemical catalyst that compound prepares.
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: take out after honeycombed cement base carrier being placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 0.5h ~ 24h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: take out after pretreated for step (1) honeycombed cement base carrier being placed in interface treating agent more than ultrasonic activation 0.5h, dry, for subsequent use;
(3) dispersion of photochemical catalyst: inserted by photochemical catalyst in the mixed solution (absolute ethyl alcohol and water are in any proportion) of absolute ethyl alcohol and water, make the concentration of photochemical catalyst at 1 ~ 10g/L, ultrasonic disperse half an hour, makes it dispersed, for subsequent use;
(4) load of photochemical catalyst: the honeycombed cement base carrier of getting after step (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, is as the criterion with submergence honeycombed cement base carrier, keep load 0 ~ 24h;
(5) take out the honeycombed cement base carrier after load, be placed in 65 DEG C ~ 105 DEG C baking ovens and dry, obtain honeycombed cement base optic catalytic material.
By such scheme, described honeycombed cement base carrier choose in silicate honeycombed cement sill, aluminium sulfate honeycombed cement sill and chlorine oxygen magnesium honeycombed cement sill any one.
By such scheme, the average pore size of described honeycombed cement base carrier is at below 2mm, and unit weight is at 1200kg/m
3below.
By such scheme, described interface treating agent is any one in alkali lye, Ludox, wherein alkali lye choose sodium hydroxide solution, potassium hydroxide solution or ammonia spirit any one, the concentration of sodium hydroxide solution, potassium hydroxide solution is 10
-4~ 10
-1mol/L, the pH value of ammonia spirit is 10 ~ 13, and Ludox solid content is 5 ~ 40%.
By such scheme, active TiO selected by described photochemical catalyst
2powder and active TiO
2in colloidal sol any one.
By such scheme, described active TiO
2powder and colloidal sol are anatase crystal or rutile/anatase mixing crystal formation, wherein active TiO
2the solid content of colloidal sol is 1% ~ 20%.
The preparation technology of described a kind of honeycombed cement base optic catalytic material, it comprises the steps:
(1) pretreatment of honeycombed cement base carrier: take out after honeycombed cement base carrier being placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 0.5h ~ 24h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: take out after above-mentioned pretreated honeycombed cement base carrier is placed in the process of interface treating agent ultrasonic activation, dries, for subsequent use;
(3) dispersion of photochemical catalyst: inserted by photochemical catalyst in the arbitrary proportion dispersion solvent of absolute ethyl alcohol and water, makes its concentration at 1 ~ 10g/L, ultrasonic disperse half an hour, makes it dispersed, for subsequent use;
(4) load of photochemical catalyst: get the honeycombed cement base carrier after above-mentioned activation and be placed in pressure vessel, then vacuumize, photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence honeycombed cement base carrier, keeps load 0 ~ 24h;
(5) take out the honeycombed cement base carrier after load, be placed in 65 DEG C ~ 180 DEG C baking ovens and dry, obtain honeycombed cement base optic catalytic material.
Compared with prior art, advantage of the present invention and beneficial effect are:
(1) the honeycombed cement base optic catalytic material that prepared by the present invention has noxious pollutant function in Cleaning Air and water body, environmental friendliness, and to environment non-secondary pollution.
(2) the present invention adopts the mode of ultrasonic perforate, improves the through-hole rate of honeycombed cement base carrier, possesses and improves pernicious gas adsorbance and the advantage to catalysis material load capacity, can improve the photocatalysis efficiency of material.
(3) the present invention adopts the mode of interface processing to activate the surface nature of honeycombed cement base carrier, is conducive to the load capacity and the interface binding power that improve catalysis material, and then improves its photocatalysis efficiency and long period of activity.
(4) the present invention adopt the mode of negative pressure load to prepare honeycombed cement base optic catalytic material in the more even and load depth of photocatalyst larger, be conducive to the overall performance improving material.
(5) the present invention is using honeycombed cement sill as supporting substrates, and compared to ordinary cement sill, its even and abundant pore structure can work in coordination with photochemical catalyst the disposal ability improved pernicious gas.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not only confined to the following examples, but meet the most wide region consistent with principles of this disclosure and features of novelty.
Pressure vessel refers to the closed container that can bear certain negative pressure, and what use in following embodiment is negative pressure of vacuum water conservation machine (steel), but pressure vessel described in these claims is not only confined to use negative pressure of vacuum water conservation machine.
embodiment 1:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: be 400kg/m by unit weight
3, average pore size is taken out after the silicate honeycombed cement sill (commercially available, silicate porous heat-insulating brick material) of below 2mm is placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 0.5h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: step (1) pretreated silicate honeycombed cement sill is placed in 10
-4take out after ultrasonic activation 1h in the sodium hydroxide solution of mol/L, dry, for subsequent use;
(3) dispersion of photochemical catalyst: nano-titanium dioxide powder is (commercially available, Degussa P25, rutile/anatase mixing crystal formation) to insert volume fraction be in the aqueous solution of 50% absolute ethyl alcohol to photochemical catalyst, make nano-titanium dioxide powder concentration at 1g/L, ultrasonic disperse half an hour, make it dispersed, for subsequent use;
(4) load of photochemical catalyst: the silicate honeycombed cement sill after step of learning from else's experience (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence silicate honeycombed cement sill, keep load 1h;
(5) take out the silicate honeycombed cement sill after step (4) load, be placed in 65 DEG C of baking ovens and dry, obtain silicate honeycombed cement base optic catalytic material.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) silicate honeycombed cement base optic catalytic material is be the degradation efficiency of 367ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 25%.
embodiment 2:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: be 400kg/m by unit weight
3, average pore size is taken out after the aluminium sulfate honeycombed cement sill (commercially available, aluminium sulfate porous heat insulation) of below 1mm is placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 12h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: 10 will be placed in through step (1) pretreated aluminium sulfate honeycombed cement sill
-1take out after ultrasonic activation 1h in the potassium hydroxide solution of mol/L, dry, for subsequent use;
(3) dispersion of photochemical catalyst: nano-titanium dioxide powder is (commercially available, Degussa P25, rutile/anatase mixing crystal formation) to insert volume fraction be in the aqueous solution of 80% absolute ethyl alcohol to photochemical catalyst, make nano-titanium dioxide powder concentration at 10g/L, ultrasonic disperse half an hour, make it dispersed, for subsequent use; (4) load of photochemical catalyst: the aluminium sulfate honeycombed cement base carrier after step of learning from else's experience (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence aluminium sulfate honeycombed cement base carrier, keep load 12h;
(5) take out the aluminium sulfate honeycombed cement base carrier after step (4) load, be placed in 85 DEG C of baking ovens and dry, obtain aluminium sulfate honeycombed cement base optic catalytic material.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) aluminium sulfate honeycombed cement base optic catalytic material is be the degradation efficiency of 349ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 50%.
embodiment 3:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: be 200kg/m by unit weight
3, average pore size is taken out after the chlorine oxygen magnesium honeycombed cement sill (commercially available, magnesia oxychloride cement porous heat insulation board) of below 0.2mm is placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 1h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: take out after being placed in the Ludox ultrasonic activation 1h of solid content 40% through step (1) pretreated chlorine oxygen magnesium honeycombed cement sill, dries, for subsequent use;
(3) dispersion of photochemical catalyst: nano-titanium dioxide powder is (commercially available, Degussa P25, rutile/anatase mixing crystal formation) to insert volume fraction be in the 95% absolute ethyl alcohol aqueous solution to photochemical catalyst, make nano-titanium dioxide powder concentration at 10g/L, ultrasonic disperse half an hour, make it dispersed, for subsequent use;
(4) load of photochemical catalyst: the chlorine oxygen magnesium honeycombed cement sill after step of learning from else's experience (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence chlorine oxygen magnesium honeycombed cement sill, keep load 12h;
(5) take out the chlorine oxygen magnesium honeycombed cement sill after step (4) load, be placed in 105 DEG C of baking ovens and dry, obtain chlorine oxygen magnesium honeycombed cement base optic catalytic material.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) chlorine oxygen magnesium honeycombed cement base optic catalytic material is be the degradation efficiency of 383ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 80%.
embodiment 4:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: be 800kg/m by unit weight
3, average pore size is taken out after the silicate honeycombed cement sill (commercially available, silicate porous heat insulation board) of below 0.5mm is placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 24h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: 10 will be placed in through step (1) pretreated silicate honeycombed cement sill
-1take out after ultrasonic activation 3h in the potassium hydroxide solution of mol/L, dry, for subsequent use;
(3) dispersion of photochemical catalyst: be the TiO of 20% by solid content
2volume fraction inserted by colloidal sol photochemical catalyst (commercially available, anatase crystal) is in the 95% absolute ethyl alcohol aqueous solution, makes the concentration of TiO 2 sol at 10g/L, ultrasonic disperse half an hour, makes it dispersed, for subsequent use;
(4) load of photochemical catalyst: the silicate honeycombed cement sill after step of learning from else's experience (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence silicate honeycombed cement sill, keep load 24h;
(5) take out the silicate honeycombed cement sill after step (4) load, be placed in 65 DEG C of baking ovens and dry, obtain silicate honeycombed cement base optic catalytic material.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) silicate honeycombed cement base optic catalytic material is be the degradation efficiency of 354ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 35%.
embodiment 5:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
Substantially the same manner as Example 4, difference is: 10
-1the ammonia spirit that the potassium hydroxide solution of mol/L is 12 by PH replaces.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) silicate honeycombed cement base optic catalytic material is be the degradation efficiency of 331ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 35%.
embodiment 6:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
(1) pretreatment of honeycombed cement base carrier: be 200kg/m by unit weight
3, average pore size is taken out after the chlorine oxygen magnesium honeycombed cement sill (commercially available, magnesia oxychloride cement porous heat insulation board) of below 0.5mm is placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 2h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: take out after being placed in the Ludox ultrasonic activation 3h of solid content 5% through step (1) pretreated chlorine oxygen magnesium honeycombed cement sill, dries, for subsequent use;
(3) dispersion of photochemical catalyst: be the TiO of 1% by solid content
2volume fraction inserted by colloidal sol photochemical catalyst (commercially available, anatase crystal) is in the 95% absolute ethyl alcohol aqueous solution, makes TiO
2collosol concentration, at 1g/L, ultrasonic disperse half an hour, makes it dispersed, for subsequent use;
(4) load of photochemical catalyst: the chlorine oxygen magnesium honeycombed cement sill after step of learning from else's experience (2) activation is placed in pressure vessel, then vacuumize, step (3) gained photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence chlorine oxygen magnesium honeycombed cement sill, keep load 2h;
(5) take out the chlorine oxygen magnesium honeycombed cement base carrier after step (4) load, be placed in 105 DEG C of baking ovens and dry, obtain chlorine oxygen magnesium honeycombed cement base optic catalytic material.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) chlorine oxygen magnesium honeycombed cement base optic catalytic material is be the degradation efficiency of 401ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 60%.
embodiment 7:
A kind of honeycombed cement base optic catalytic material, it prepares in accordance with the following steps:
Substantially the same manner as Example 4, difference is: unit weight is 800kg/m
3, average pore size is 1200kg/m at the silicate honeycombed cement sill of below 0.5mm by unit weight
3, average pore size replaces at the silicate honeycombed cement sill of below 0.5mm.
With 125W high pressure mercury fluorescent lamp (Philip GYZ125E) for light source, gas chromatograph (GC 9650) is testing equipment, test 40mm × 40mm(is long × wide) silicate honeycombed cement base optic catalytic material is be the degradation efficiency of 373ppm acetone to concentration in 7.2L closed container at volume, through the photocatalytic degradation of 50min, its degradation efficiency can reach more than 15%.
Claims (4)
1. a honeycombed cement base optic catalytic material, is characterized in that it is prepared by honeycombed cement base carrier, interface treating agent and photochemical catalyst and obtains; Described honeycombed cement base carrier choose in silicate honeycombed cement sill, aluminium sulfate honeycombed cement sill and chlorine oxygen magnesium honeycombed cement sill any one; Described interface treating agent is alkali lye; Described alkali lye be sodium hydroxide solution, potassium hydroxide solution or ammonia spirit any one, wherein the concentration of sodium hydroxide solution, potassium hydroxide solution is 10
-4~ 10
-1mol/L, the pH value of ammonia spirit is 10 ~ 13.
2. a kind of honeycombed cement base optic catalytic material according to claim 1, it is characterized in that the average pore size of described honeycombed cement base carrier is at below 2mm, unit weight is less than 1200kg/m
3.
3. a kind of honeycombed cement base optic catalytic material according to claim 1, is characterized in that active TiO selected by described photochemical catalyst
2powder and active TiO
2in colloidal sol any one, wherein active TiO
2powder and colloidal sol choose anatase crystal or rutile/anatase mixing crystal formation, active TiO
2the solid content of colloidal sol is 1% ~ 20%.
4. the preparation technology of a kind of honeycombed cement base optic catalytic material as claimed in claim 1, is characterized in that it comprises the steps:
(1) pretreatment of honeycombed cement base carrier: take out after honeycombed cement base carrier being placed in the ultrasonic cleaning of ultrasonic cleaning instrument and ultrasonic perforate 0.5h ~ 24h, dries, for subsequent use;
(2) the interface activation process of honeycombed cement base carrier: take out after above-mentioned pretreated honeycombed cement base carrier is placed in the process of interface treating agent ultrasonic activation, dries, for subsequent use;
(3) dispersion of photochemical catalyst: inserted by photochemical catalyst in the arbitrary proportion dispersion solvent of absolute ethyl alcohol and water, makes its concentration at 1 ~ 10g/L, ultrasonic disperse half an hour, makes it dispersed, for subsequent use;
(4) load of photochemical catalyst: get the honeycombed cement base carrier after above-mentioned activation and be placed in pressure vessel, then vacuumize, photocatalyst dispersion liquid is injected the pressure vessel after vacuum, be as the criterion with submergence honeycombed cement base carrier, keep load 0 ~ 24h, the time keeping load is not 0;
(5) take out the honeycombed cement base carrier after load, be placed in 65 DEG C ~ 180 DEG C baking ovens and dry, obtain honeycombed cement base optic catalytic material.
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| CN104649365A (en) * | 2015-01-28 | 2015-05-27 | 河海大学 | TiO2/ foam concrete panel snake-shaped ultraviolet sterilization device for sewage |
| US11452988B2 (en) | 2015-02-27 | 2022-09-27 | Photocat A/S | Photocatalytic concrete product and a method to produce a photocatalytic concrete product |
| CN108636391A (en) * | 2018-04-29 | 2018-10-12 | 华中科技大学 | A kind of load type titanium dioxide photocatalytic material and preparation method thereof |
| CN112516985A (en) * | 2020-11-12 | 2021-03-19 | 南京国兴环保产业研究院有限公司 | Photocatalyst-loaded supercritical foaming material and preparation method thereof |
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| JP2002274965A (en) * | 2001-03-12 | 2002-09-25 | Ishikawajima Harima Heavy Ind Co Ltd | Porous concrete |
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